The construction and the electrochemical characteristics of novel freestanding biomedical polymer-single walled carbon nanotube (SWCNT) nanocomposite electrode, formed via an intercalation process have been described. The intercalating polymer reinforces the Buckypaper to provide sufficient strength and flexibility. The intercalated platforms represent randomly dispersed CNT bundles and individual CNTs which are partially surrounded by an insulating polymer. This arrangement leads to an improvement in the Faradaic to capacitive charging ratio, relative to electrodes derived from non-intercalated samples. The electrochemical behaviour of freestanding SIBS intercalated SWCNT electrodes have been investigated via analysis of dc and Fourier transformed (FT) ac voltammetries in order to determine the composites ability to serve as an electrode platform. Comparison of experimental data with simulated dc and FT ac cyclic voltammograms are considered with the structure of SIBS intercalated SWCNT sheets producing random arrays of nano-/miro-electrode domains derived from individual CNTs/CNT bundles. In comparison with the bare sample, significantly faster electron transfer reaction rates and improved Faradaic to capacitive background charging current ratios, suggest that the devices made from this novel nanocomposite electrode should offer improved performance in electroanalytical applications, and possibility also in bio-/chemo-sensors, biofuel cell type devices and as a biocompatible platform for cell culturing.